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EP3063191B1 - Polymers containing s-vinylthioalkanoles - Google Patents

Polymers containing s-vinylthioalkanoles Download PDF

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Publication number
EP3063191B1
EP3063191B1 EP14780872.9A EP14780872A EP3063191B1 EP 3063191 B1 EP3063191 B1 EP 3063191B1 EP 14780872 A EP14780872 A EP 14780872A EP 3063191 B1 EP3063191 B1 EP 3063191B1
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EP
European Patent Office
Prior art keywords
vinyl
monomer
process according
thioethan
mol
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EP14780872.9A
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German (de)
French (fr)
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EP3063191A1 (en
Inventor
Friederike Fleischhaker
Christian Schade
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • C08F228/04—Thioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

Definitions

  • the present invention relates to processes for the preparation of polymers containing S-vinylthioalkanol as a monomer.
  • Articles of the invention further polymers are prepared according to such methods and specific copolymers. Further objects of the invention are the uses of such polymers and mixtures containing such polymers.
  • Reactive monomers having alkoxylate substituents find applications in a wide variety of technical fields, for example as a concrete plasticizer or as a component of paints, paints and varnishes.
  • a known reactive monomer is 4-hydroxybutyl vinyl ether (HBVE).
  • HBVE 4-hydroxybutyl vinyl ether
  • the radical homopolymerization of vinyl ethers usually leads only to oligomers. Water is not useful as a solvent because of the high susceptibility to hydrolysis of vinyl ethers as a solvent.
  • S-vinylthioalkanols are also useful as reactive monomers with alkoxylate substituents.
  • Copolymers of S-vinyl-2-thioethan-1-ol with N-vinylpyrrolidone are made Vorobeva et al., Vysokomolekulyarne Soedineniya Ser. B, 46, 1239-1243 (2004 ) known. These copolymers are prepared in bulk or in solvents. The solvent is also called water.
  • Copolymers of S-vinyl-2-thioethane-1-ol with N, N-dimethyl-N, N-diallylammonium chloride are made Vorobeva et al., Vysokomolekulyarne Soedineniya Ser. B, 46, 364-368 (2004 ) known.
  • Copolymers of S-vinyl-2-thioethan-1-ol with methyl methacrylate, acrylamide and acrylonitriles, which are mass-produced, are known from the DE 2055893 A1 known.
  • Copolymers of S-vinyl-2-thioethan-1-ol with styrene and acrylates prepared in organic solvents are known from the DE 2128681 A1 known.
  • the object of the present invention was to provide polymers which do not have the abovementioned disadvantages.
  • a partial object of the invention was to develop reactive monomers with alkoxylate substituents for an efficient polymerization reaction.
  • those compounds should be provided which have increased hydrolytic stability both as a monomer and as polymerized into the polymer.
  • S-vinylthioalkanols are commercially available or may be prepared, for example, from ethyne (acetylene) and thioalcohols by the Reppe method or other methods known to those skilled in the art.
  • Expressions of the form C a -C b designate in the context of this invention chemical compounds or substituents with a certain number of carbon atoms.
  • the number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a.
  • Further specification of the chemical compounds or substituents is made by terms of the form C a -C b -V.
  • V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
  • the S-vinylthioalkanol is selected from the group consisting of S-vinyl-2-thioethane-1-ol, S-vinyl-2-thiopropan-1-ol, S-vinyl-1-thiopropan-2-ol, S Vinyl-2-thiobutan-1-ol, S-vinyl-1-thiobutan-2-ol, S-vinyl-2-thiopentan-1-ol, S-vinyl-1-thiopentan-2-ol, S-vinyl 2-thiocyclohexan-1-ol, S-vinyl-2-thio (C 12 -C 22 ) -1-ol, S-vinyl-1-thio (C 12 -C 22 ) -2-ol, S Vinyl-1-thiopropane-2,3-diol, S-vinyl-2-thiopropane-1,3-diol, 1-phenyl-S-vinyl-1-thio-
  • the S-vinylthioalkanol is selected from the group consisting of S-vinyl-2-thioethan-1-ol, S-vinyl-1-thiopropan-2-ol, S-vinyl-1-thiopropane-2,3-diol,
  • the S-vinylthioalkanol is particularly preferably S-vinyl-2-thioethane-1-ol.
  • At least one further monomer other than an S-vinylthioalkanol is used to prepare the polymers, as already mentioned, with the proviso that no N-vinylpyrrolidone is used as the monomer for the preparation of the polymers.
  • a monoethylenically unsaturated water-soluble monomer is preferably used as at least one further monomer.
  • a monoethylenically unsaturated water-soluble monomer selected from the group consisting of monoethylenically unsaturated water-soluble monomer having one or more acid groups, monoethylenically unsaturated water-soluble monomer having one or more ester groups, monoethylenically unsaturated water-soluble monomer having one or more amide groups, monoethylenically unsaturated water-soluble monomer one or more anhydride groups, monoethylenically unsaturated water-soluble monomer having one or more quaternized nitrogen groups, monoethylenically unsaturated water-soluble monomer having one or more heteroaromatic groups.
  • Particularly preferred monoethylenically unsaturated water-soluble monomers are (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, vinylphosphonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Vinylimidazole, tri (m) ethylammonium ethyl (meth) acrylate with counter ion chloride, methylsulfate, tri (m) ethylammonium ethyl / propyl (meth) acrylamide with counterion chloride, methylsulfate, methyl, alkyl (PEG) x , (x is a number from 200 to 10,000), hydroxyethyl, hydroxypropyl, dimethylaminoethyl, ureido (meth) acrylate, (meth) acrylamide, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, methacrylamido-e
  • acrylic acid is used as the monoethylenically unsaturated monomer.
  • S-vinyl-2-thioethan-1-ol and acrylic acid no further monomers are used for the preparation of the polymers.
  • the polymers produced have an upper critical solution temperature (UCST) in water of 0 to 99 ° C., preferably from room temperature (21 ° C.) to 90 ° C., in particular from 30 to 80 ° C.
  • UST upper critical solution temperature
  • a further advantage of the process according to the invention is that it makes it possible to prepare polymers or copolymers with a readily controllable UCST, in particular a UCST in water.
  • the height of the UCST is set here via the acrylic acid fraction.
  • a polymer of S-vinyl-2-thioethane-1-ol / acrylic acid has a UCST in water of about 50 ° C
  • a polymer of S-vinyl-2-thioethan-1-ol Acrylic acid (40/60 molar ratio) has a UCST of about 37 ° C
  • a polymer of S-vinyl-2-thioethane-1-ol / acrylic acid (20/80 molar ratio) is completely soluble in water.
  • a homopolymer of S-vinyl-2-thioethan-1-ol is not soluble in water, but in contrast is present only as a suspension in water.
  • the amount of S-vinylthioalkanol used in the process of the invention may vary over a wide range depending on the application of the polymer. In the context of the process according to the invention, as a rule from 1 to 99 mol% of S-vinylthioalkanol, preferably from 20 to 80 mol%, particularly preferably from 30 to 70 mol%, based on the total amount of monomers used.
  • from 1 to 99 mol% of S-vinyl-2-thioethane-1-ol preferably from 20 to 80 mol%, particularly preferably from 30 to 70 mol%, and from 99 to 1 mol% is preferred in the process according to the invention to 20 mol%, particularly preferably 70 to 30 mol%, of further monomers based on the total amount of monomers.
  • from 1 to 99 mol% of S-vinyl-2-thioethane-1-ol preferably from 20 to 80 mol%, more preferably from 30 to 70 mol%, and from 99 to 1 mol%, preferably from 80 used to 20 mol%, particularly preferably from 70 to 30 mol% of acrylic acid based on the total amount of monomers.
  • Another object of the invention are polymers prepared by the process according to the invention, preferably hydrolysis-stable polymers.
  • Another object of the invention are copolymers, preferably hydrolysis-stable copolymers consisting of S-vinyl-2-thioethan-1-ol and one or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid, itaconic acid, maleic acid, maleic anhydride, vinylphosphonic acid. Preference is given to copolymers consisting of S-vinyl-2-thioethane-1-ol and acrylic acid.
  • Another object of the invention are mixtures, preferably aqueous compositions containing the above-mentioned polymers, which were prepared by the process according to the invention.
  • aqueous compositions which contain at least 50% by weight of water, particularly preferably at least 80% by weight of water, in particular 100% by weight of water, based on the total amount of solvent.
  • These mixtures or aqueous compositions have a pH of from 2 to 10, particularly preferably a pH of from 4 to 8, in particular a pH of from 5 to 7.
  • the invention further provides the use of the abovementioned polymers prepared by the process according to the invention or of mixtures, preferably aqueous compositions containing such polymers as concrete plasticizers, wetting agents, in cosmetics, as adhesive components, in emulsion polymerization, for metal surface treatment , in coating applications, in paints, in detergents, in dishwashing detergents, as encapsulating material or wrapping material.
  • aqueous compositions containing such polymers as concrete plasticizers, wetting agents, in cosmetics, as adhesive components, in emulsion polymerization, for metal surface treatment , in coating applications, in paints, in detergents, in dishwashing detergents, as encapsulating material or wrapping material.
  • the present invention provides reactive hydrolysis-stable S-vinylthioalkanols which can be efficiently reacted to give hydrolysis-stable polymers and copolymers.
  • the polymers and copolymers are also largely stable to bases and acids with respect to hydrolysis at the hydroxyalkyl group.
  • the S-vinylthioalkanols are therefore suitable, for example, as hydrolysis-stable replacement of hydroxyalkyl (meth) acrylates.
  • hydroxyethyl acrylate is approximately 70% hydrolyzed after 60 minutes; S-vinyl-2-thioethane-1-ol barely hydrolyzes under these basic conditions.
  • these monomers are stable in the free-radical polymerization in aqueous solution and the resulting polymers when stored in aqueous solution.
  • analogous vinyl ether alcohols are not stable to hydrolysis on radical polymerisation in water - acetaldehyde and the corresponding diol are formed in the presence of acids, but not a polymer.
  • S-vinylthioalkanols are even stable to hydrolysis upon copolymerization (even with acids such as acrylic acid or itaconic acid) and storage of the copolymers in aqueous solution.
  • the K values were after H. Fikentscher, Cellulose Chemistry, Vol. 13, pages 58 to 64 and 71 to 74 (1932 ) in 1 wt .-% aqueous or methanolic solution at 25 ° C.
  • the template was sparged with nitrogen for 15 minutes and heated to 70 ° C. under a nitrogen atmosphere. Subsequently, the remainder of feed 1 and of feed 2 and within 4 hours the remainder of feed 3 was added dropwise within 3 hours.
  • Mn was determined to be 3348 g / mol, Mw to 6026 g / mol, and PDI (Mw / Mn) to 1.8 (calibration curve for PMMA).
  • the upper critical solution temperature (UCST) of the copolymer in water was about 50 ° C.
  • the template was sparged with nitrogen for 15 minutes and heated to 70 ° C. under a nitrogen atmosphere. Subsequently, the remainder of feed 1 and of feed 2 and within 4 hours the remainder of feed 3 was added dropwise within 3 hours.
  • the upper critical solution temperature (UCST) of the copolymer in water was about 37 ° C.
  • the template was sparged with nitrogen for 15 minutes and heated to 70 ° C. under a nitrogen atmosphere. Subsequently, the remainder of feed 1 and within 4 hours the remainder of feed 2 were added dropwise within 3 hours. Thereafter, the mixture was stirred at 70 ° C for 2 hours. Subsequently, feed 3 was added dropwise within 45 min and stirred at 70 ° C for 2 hours.
  • the residual monomer content was about 2 mol%, based on the total amount of monomers used.
  • Mn was determined to be 6718 g / mol per GPC, Mw to 16680 g / mol and PDI to 2.5. (Calibration curve for PMMA).
  • the template was sparged with nitrogen for 15 minutes and heated to 88 ° C under a nitrogen atmosphere. Subsequently, the remainder of feed 1 was added dropwise within 3 hours, and the remainder of feed 2 was added dropwise within 4 hours. Thereafter, the mixture was stirred at 88 ° C for 2 hours.
  • the template was sparged with nitrogen for 15 minutes and heated to 88 ° C under a nitrogen atmosphere. Subsequently, the remainder of feed 1 was added dropwise within 3 hours, and the remainder of feed 2 was added dropwise within 4 hours. Thereafter, the mixture was stirred at 88 ° C for 2 hours.
  • copolymers of Examples 4 and 5 were used to coat hot galvanized steel test panels (Gardobond OE HDG 3, 105 x 190 m).
  • test panels were immersed in a mildly alkaline cleaner solution (Surtech 133, Surtech) for 30 seconds, rinsed immediately with demineralized water and then dried with nitrogen.
  • the cleaned sheets were immersed for 1 second in a 25 wt .-% aqueous solution of the copolymer, squeezed off with a roller system and dried for 12 seconds at 160 ° C in a convection oven.
  • the peak metal temperature (PMT) did not exceed 50 ° C.
  • test panels thus obtained were examined for their corrosion resistance in a salt spray test according to DIN EN ISO 9227.
  • polymer Corroded area after salt spray test no coating 100% (completely corroded)

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Description

Die vorliegende Erfindung betrifft Verfahren zur Herstellung von Polymeren enthaltend S-Vinylthioalkanol als Monomer. Gegenstände der Erfindung sind weiterhin Polymere hergestellt gemäß solchen Verfahren und spezielle Copolymere. Weitere Gegenstände der Erfindung sind die Verwendungen solcher Polymere und Mischungen enthaltend solche Polymere.The present invention relates to processes for the preparation of polymers containing S-vinylthioalkanol as a monomer. Articles of the invention further polymers are prepared according to such methods and specific copolymers. Further objects of the invention are the uses of such polymers and mixtures containing such polymers.

Weitere Ausführungsformen der vorliegenden Erfindung sind den Ansprüchen, der Beschreibung und den Beispielen zu entnehmen. Es versteht sich, dass die vorstehend genannten und die nachstehend noch zu erläuternden Merkmale des erfindungsgemäßen Gegenstandes nicht nur in der jeweils konkret angegebenen Kombination, sondern auch in anderen Kombinationen verwendbar sind, ohne den Rahmen der Erfindung zu verlassen. Bevorzugt beziehungsweise ganz bevorzugt sind insbesondere auch diejenigen Ausführungsformen der vorliegenden Erfindung, in denen alle Merkmale des erfindungsgemäßen Gegenstandes die bevorzugten beziehungsweise ganz bevorzugten Bedeutungen haben.Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular concretely specified combination but also in other combinations without departing from the scope of the invention. In particular, those embodiments of the present invention in which all features of the article according to the invention have the preferred or very preferred meanings are preferred or very particularly preferred.

Reaktive Monomere mit Alkoxylatsubstituenten finden in den unterschiedlichsten technischen Gebieten Anwendungen, beispielsweise als Betonverflüssiger oder als Bestandteil von Anstrichen, Farben und Lacken. Ein bekanntes reaktives Monomer ist 4-Hydroxybutylvinylether (HBVE). Die radikalische Homopolymerisation von Vinylethern führt in der Regel nur zu Oligomeren. Wasser ist als Lösungsmittel wegen der hohen Hydrolyseanfälligkeit der Vinylether nicht als Lösungsmittel zu gebrauchen.Reactive monomers having alkoxylate substituents find applications in a wide variety of technical fields, for example as a concrete plasticizer or as a component of paints, paints and varnishes. A known reactive monomer is 4-hydroxybutyl vinyl ether (HBVE). The radical homopolymerization of vinyl ethers usually leads only to oligomers. Water is not useful as a solvent because of the high susceptibility to hydrolysis of vinyl ethers as a solvent.

S-Vinylthioalkanole eignen sich ebenfalls als Reaktive Monomere mit Alkoxylatsubstituenten.S-vinylthioalkanols are also useful as reactive monomers with alkoxylate substituents.

Copolymere von S-Vinyl-2-thioethan-1-ol mit N-vinylpyrrolidon sind aus Vorob'eva et al., Vysokomolekulyarne Soedineniya Ser. B, 46, 1239-1243 (2004 ) bekannt. Diese Copolymere werden in Masse oder in Lösungsmitteln hergestellt. Als Lösungsmittel ist auch Wasser genannt.Copolymers of S-vinyl-2-thioethan-1-ol with N-vinylpyrrolidone are made Vorobeva et al., Vysokomolekulyarne Soedineniya Ser. B, 46, 1239-1243 (2004 ) known. These copolymers are prepared in bulk or in solvents. The solvent is also called water.

Copolymere von S-Vinyl-2-thioethan-1-ol mit N,N-dimethyl-N,N-diallylammonium-chlorid sind aus Vorob'eva et al., Vysokomolekulyarne Soedineniya Ser. B, 46, 364-368 (2004 ) bekannt.Copolymers of S-vinyl-2-thioethane-1-ol with N, N-dimethyl-N, N-diallylammonium chloride are made Vorobeva et al., Vysokomolekulyarne Soedineniya Ser. B, 46, 364-368 (2004 ) known.

Copolymere von S-Vinyl-2-thioethan-1-ol mit Methyl-Methacrylat, Acrylamid und Acrylonitrile, die in Masse hergestellt werden, sind aus der DE 2055893 A1 bekannt.Copolymers of S-vinyl-2-thioethan-1-ol with methyl methacrylate, acrylamide and acrylonitriles, which are mass-produced, are known from the DE 2055893 A1 known.

Copolymere von S-Vinyl-2-thioethan-1-ol mit Styrol und Acrylaten, hergestellt in organischen Lösungsmitteln sind aus der DE 2128681 A1 bekannt.Copolymers of S-vinyl-2-thioethan-1-ol with styrene and acrylates prepared in organic solvents are known from the DE 2128681 A1 known.

Weiterhin bekannt sind aus Vorob'eva et al., Vysokomolekulyarne Soedineniya Ser. B, 45, 700-704 (2003 ) Copolymere mit Acrylamid, Styrol und Methyl-Methacrylate, die in DMSO als Lösungsmittel hergestellt werden.
Bei den Polymeren des Standes der Technik treten Probleme bei der Herstellung auf. Beispielsweise zeigen Vinylether bei der Polymerisation oder Copolymerisation keine besonders hohe Reaktivität und führen auch zu einigen Nebenreaktionen. Einige der Vinylether, beispielsweise HBVE, sind insbesondere im sauren Milieu nur bedingt hydrolysestabil.Furthermore, are known Vorobeva et al., Vysokomolekulyarne Soedineniya Ser. B, 45, 700-704 (2003 ) Copolymers with acrylamide, styrene and methyl methacrylates, which are prepared in DMSO as a solvent.
The polymers of the prior art have problems in the production. For example, vinyl ethers show no particularly high reactivity during the polymerization or copolymerization and also lead to some side reactions. Some of the vinyl ethers, for example HBVE, are only partially stable to hydrolysis, especially in an acidic medium.

Aufgabe der vorliegenden Erfindung war es Polymere bereit zu stellen, die die oben genannten Nachteile nicht aufweisen. Eine Teilaufgabe der Erfindung war es für eine effiziente Polymerisationsreaktion reaktive Monomere mit Alkoxylatsubstituenten zu entwickeln. Als eine weitere Teilaufgabe der vorliegenden Erfindung sollten solche Verbindungen bereitgestellt werden, die sowohl als Monomer, als auch einpolymerisiert in das Polymer eine erhöhte Hydrolysestabilität aufweisen.The object of the present invention was to provide polymers which do not have the abovementioned disadvantages. A partial object of the invention was to develop reactive monomers with alkoxylate substituents for an efficient polymerization reaction. As a further sub-task of the present invention, those compounds should be provided which have increased hydrolytic stability both as a monomer and as polymerized into the polymer.

Diese und andere Aufgaben werden, wie aus dem Offenbarungsgehalt der vorliegenden Erfindung ersichtlich, durch die verschiedenen Ausführungsformen der Erfindung gelöst, insbesondere durch Verfahren zur Herstellung von Polymeren enthaltend S-Vinylthioalkanol als Monomer durch radikalische Polymerisation, wobei die Polymerisation in wässriger Lösung durchgeführt wird, unter der Maßgabe, dass zur Herstellung der Polymere kein N-Vinylpyrrolidon als Monomer eingesetzt wird, bevorzugt in einer wässrigen Lösung deren Lösungsmittelgemisch mindestens 50 Gew.-% Wasser enthält, besonders bevorzugt mindestens 80 Gew.-% Wasser, insbesondere 100 Gew.-% Wasser, jeweils bezogen auf das Lösemittelgemisch.These and other objects are achieved, as apparent from the disclosure of the present invention, by the various embodiments of the invention, in particular by methods for the preparation of polymers containing S-vinylthioalkanol as a monomer by radical polymerization, wherein the polymerization is carried out in aqueous solution with the proviso that no N-vinylpyrrolidone is used as monomer for preparing the polymers, preferably in an aqueous solution whose solvent mixture contains at least 50 wt .-% water, more preferably at least 80 wt .-% water, in particular 100 wt .-% water , in each case based on the solvent mixture.

S-Vinylthioalkanole sind kommerziell erhältlich oder können beispielsweise aus Ethin (Acetylen) und Thioalkoholen nach dem Reppe Verfahren oder anderen dem Fachmannn bekannten Verfahren hergestellt werden.S-vinylthioalkanols are commercially available or may be prepared, for example, from ethyne (acetylene) and thioalcohols by the Reppe method or other methods known to those skilled in the art.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden als S-Vinylthioalkanol ungesättigte Verbindungen der allgemeinen Formel (I) eingesetzt

Figure imgb0001
wobei

R1, R2, R3
unabhängig voneinander, gleich oder verschieden, H, CH3, bevorzugt H,
R4
lineares oder verzweigtes C1-C30-Alkylen, bevorzugt C2-C10-Alkylen, besonders bevorzugt C2-C4-Alkylen, insbesondere -CH2-CH2-,
bedeuten.In a preferred embodiment of the process according to the invention, unsaturated compounds of the general formula (I) are used as S-vinylthioalkanol
Figure imgb0001
 in which
R 1 , R 2 , R 3
independently of one another, the same or different, H, CH 3 , preferably H,
R 4
linear or branched C 1 -C 30 -alkylene, preferably C 2 -C 10 -alkylene, more preferably C 2 -C 4 -alkylene, in particular -CH 2 -CH 2 -,
mean.

Ausdrücke der Form Ca-Cb bezeichnen im Rahmen dieser Erfindung chemische Verbindungen oder Substituenten mit einer bestimmten Anzahl von Kohlenstoffatomen. Die Anzahl an Kohlenstoffatomen kann aus dem gesamten Bereich von a bis b, einschließlich a und b gewählt werden, a ist mindestens 1 und b immer größer als a. Eine weitere Spezifizierung der chemischen Verbindungen oder der Substituenten erfolgt durch Ausdrücke der Form Ca-Cb-V. V steht hierbei für eine chemische Verbindungsklasse oder Substituentenklasse, beispielsweise für Alkylverbindungen oder Alkylsubstituenten.Expressions of the form C a -C b designate in the context of this invention chemical compounds or substituents with a certain number of carbon atoms. The number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a. Further specification of the chemical compounds or substituents is made by terms of the form C a -C b -V. V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.

Im Einzelnen haben die für die verschiedenen Substituenten angegebenen Sammelbegriffe folgende Bedeutung:

  • C1-C30-Alkylen: geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen, beispielsweise C1-C10-Alkylen oder C11-C20-Alkylen, bevorzugt C1-C10-Alkylen, insbesondere Methylen, Dimethylen, Trimethylen, Tetramethylen, Pentamethylen oder Hexamethylen.
In detail, the collective terms given for the various substituents have the following meaning:
  • C 1 -C 30 -alkylene: straight-chain or branched hydrocarbon radicals having 1 to 30 carbon atoms, for example C 1 -C 10 -alkylene or C 11 -C 20 -alkylene, preferably C 1 -C 10 -alkylene, in particular methylene, dimethylene, trimethylene , Tetramethylene, pentamethylene or hexamethylene.

Besonders bevorzugt wird der S-Vinylthioalkanol gewählt aus der Gruppe bestehend aus S-Vinyl-2-thioethan-1-ol, S-Vinyl-2-thiopropan-1-ol, S-Vinyl-1-thiopropan-2-ol, S-Vinyl-2-thiobutan-1-ol, S-Vinyl-1-thiobutan-2-ol, S-Vinyl-2-thiopentan-1-ol, S-Vinyl-1-thiopentan-2-ol, S-Vinyl-2-thiocyclohexan-1-ol, S-Vinyl-2-thio-(C12-C22)-1-ol, S-Vinyl-1-thio-(C12-C22)-2-ol, S-Vinyl-1-thiopropan-2,3-diol, S-Vinyl-2-thiopropan-1,3-diol, 1-Phenyl-S-vinyl-1-thio-ethan-2-ol, 1-Phenyl-S-vinyl-2-thioethan-1-ol. Bevorzugt wird der S-Vinylthioalkanol gewählt aus der Gruppe bestehend aus S-Vinyl-2-thioethan-1-ol, S-Vinyl-1-thiopropan-2-ol, S-Vinyl-1-thiopropan-2,3-diol, besonders bevorzugt ist der S-Vinylthioalkanol S-Vinyl-2-thioethan-1-ol.Particularly preferably, the S-vinylthioalkanol is selected from the group consisting of S-vinyl-2-thioethane-1-ol, S-vinyl-2-thiopropan-1-ol, S-vinyl-1-thiopropan-2-ol, S Vinyl-2-thiobutan-1-ol, S-vinyl-1-thiobutan-2-ol, S-vinyl-2-thiopentan-1-ol, S-vinyl-1-thiopentan-2-ol, S-vinyl 2-thiocyclohexan-1-ol, S-vinyl-2-thio (C 12 -C 22 ) -1-ol, S-vinyl-1-thio (C 12 -C 22 ) -2-ol, S Vinyl-1-thiopropane-2,3-diol, S-vinyl-2-thiopropane-1,3-diol, 1-phenyl-S-vinyl-1-thio-ethan-2-ol, 1-phenyl-S -vinyl-2-thioethane-1-ol. Preferably, the S-vinylthioalkanol is selected from the group consisting of S-vinyl-2-thioethan-1-ol, S-vinyl-1-thiopropan-2-ol, S-vinyl-1-thiopropane-2,3-diol, The S-vinylthioalkanol is particularly preferably S-vinyl-2-thioethane-1-ol.

In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird mindestens ein weiteres von einem S-Vinylthioalkanol verschiedenes Monomer zur Herstellung der Polymere eingesetzt, wie bereits erwähnt unter der Maßgabe, dass zur Herstellung der Polymere kein N-Vinylpyrrolidon als Monomer eingesetzt wird.In a further preferred embodiment of the process according to the invention, at least one further monomer other than an S-vinylthioalkanol is used to prepare the polymers, as already mentioned, with the proviso that no N-vinylpyrrolidone is used as the monomer for the preparation of the polymers.

Bevorzugt wird als mindestens ein weiteres Monomer ein monoethylenisch ungesättigtes wasserlösliches Monomer, ausgenommen Vinylpyrrolidon, eingesetzt. Besonders bevorzugt wird das ein monoethylenisch ungesättigte wasserlösliche Monomer gewählt aus der Gruppe bestehend aus monoethylenisch ungesättigtes wasserlösliches Monomer mit einer oder mehrerer Säuregruppen, monoethylenisch ungesättigtes wasserlösliches Monomer mit einer oder mehrerer Estergruppen, monoethylenisch ungesättigtes wasserlösliches Monomer mit einer oder mehrerer Amidgruppen, monoethylenisch ungesättigtes wasserlösliches Monomer mit einer oder mehrerer Anhydridgruppen, monoethylenisch ungesättigtes wasserlösliches Monomer mit einer oder mehrerer quarternierter Stickstoffgruppen, monoethylenisch ungesättigtes wasserlösliches Monomer mit einer oder mehrerer Heteroaromatengruppen. Insbesondere bevorzugt sind als monoethylenisch ungesättigte wasserlösliche Monomere (Meth)acrylsäure, Maleinsäure, Maleinsäureanhydrid, Itaconsäure, Vinylphosphonsäure, 2-Acrylamido-2-methylpropansulfonsäure, Vinylimidazol, Tri(m)ethylammonium-ethyl-(meth)acrylat mit Gegenion Chlorid, Methylsulfat, Tri(m)ethylammonium-Ethyl/Propyl-(meth)acrylamid mit Gegenion Chlorid, Methylsulfat, Methyl-, Alkyl-(PEG)x-, (x ist eine Zahl von 200 bis 10000), Hydroxyethyl-, Hydroxypropyl-, Dimethylaminoethyl-, Ureido(meth)acrylat, (Meth)Acrylamid, Dimethyl(meth)acrylamid, Dimethylaminopropyl(meth)acrylamid, Methacrylamido-ethyl-ethylenharnstoff oder N-Vinylformamid.A monoethylenically unsaturated water-soluble monomer, with the exception of vinylpyrrolidone, is preferably used as at least one further monomer. Particularly preferred is a monoethylenically unsaturated water-soluble monomer selected from the group consisting of monoethylenically unsaturated water-soluble monomer having one or more acid groups, monoethylenically unsaturated water-soluble monomer having one or more ester groups, monoethylenically unsaturated water-soluble monomer having one or more amide groups, monoethylenically unsaturated water-soluble monomer one or more anhydride groups, monoethylenically unsaturated water-soluble monomer having one or more quaternized nitrogen groups, monoethylenically unsaturated water-soluble monomer having one or more heteroaromatic groups. Particularly preferred monoethylenically unsaturated water-soluble monomers are (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, vinylphosphonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Vinylimidazole, tri (m) ethylammonium ethyl (meth) acrylate with counter ion chloride, methylsulfate, tri (m) ethylammonium ethyl / propyl (meth) acrylamide with counterion chloride, methylsulfate, methyl, alkyl (PEG) x , (x is a number from 200 to 10,000), hydroxyethyl, hydroxypropyl, dimethylaminoethyl, ureido (meth) acrylate, (meth) acrylamide, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, methacrylamido-ethyl-ethyleneurea or N-vinyl formamide.

In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird als monoethylenisch ungesättigtes Monomer Acrylsäure eingesetzt. Insbesondere werden neben S-Vinyl-2-thioethan-1-ol und Acrylsäure keine weiteren Monomere zur Herstellung der Polymere eingesetzt.In a particularly preferred embodiment of the process according to the invention, acrylic acid is used as the monoethylenically unsaturated monomer. In particular, in addition to S-vinyl-2-thioethan-1-ol and acrylic acid, no further monomers are used for the preparation of the polymers.

In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens weisen die hergestellten Polymere eine obere kritische Lösungstemperatur (upper critical solution temperature, UCST) in Wasser von 0 bis 99 °C auf, bevorzugt von Raumtemperatur (21 °C) bis 90 °C, insbesondere von 30 bis 80 °C.In a further embodiment of the process according to the invention, the polymers produced have an upper critical solution temperature (UCST) in water of 0 to 99 ° C., preferably from room temperature (21 ° C.) to 90 ° C., in particular from 30 to 80 ° C.

Ein weiterer Vorteil des erfindungsgemäßen Verfahrens ist, dass es gestattet Polymere bzw. Copolymere mit einer gut kontrollierbaren UCST herzustellen, insbesondere einer UCST in Wasser. Insbesondere trifft dies auf Copolymere bestehend aus Acrylsäure und S-Vinyl-2-thioethan-1-ol zu. Die Höhe der UCST wird hierbei über den Acrylsäureanteil eingestellt. Ein Polymer aus S-Vinyl-2-thioethan-1-ol/Acrylsäure (50/50 - Molverhältnis) weist ein UCST in Wasser von ca. 50°C auf, ein Polymer aus S-Vinyl-2-thioethan-1-ol/Acrylsäure (40/60 - Molverhältnis) weist eine UCST von ca. 37°C auf und ein Polymer aus S-Vinyl-2-thioethan-1-ol/Acrylsäure (20/80 - Molverhältnis) ist komplett in Wasser löslich. Ein Homopolymer aus S-Vinyl-2-thioethan-1-ol ist in Wasser nicht löslich, sondern liegt im Gegensatz hierzu nur als Suspension in Wasser vor.A further advantage of the process according to the invention is that it makes it possible to prepare polymers or copolymers with a readily controllable UCST, in particular a UCST in water. In particular, this applies to copolymers consisting of acrylic acid and S-vinyl-2-thioethan-1-ol. The height of the UCST is set here via the acrylic acid fraction. A polymer of S-vinyl-2-thioethane-1-ol / acrylic acid (50/50 molar ratio) has a UCST in water of about 50 ° C, a polymer of S-vinyl-2-thioethan-1-ol Acrylic acid (40/60 molar ratio) has a UCST of about 37 ° C and a polymer of S-vinyl-2-thioethane-1-ol / acrylic acid (20/80 molar ratio) is completely soluble in water. A homopolymer of S-vinyl-2-thioethan-1-ol is not soluble in water, but in contrast is present only as a suspension in water.

Die Menge an S-Vinylthioalkanol, die im erfindungsgemäßen Verfahren zum Einsatz kommt, kann je nach Anwendung des Polymeren über einen weiten Bereich variieren. Im Rahmen des erfindungsgemäßen Verfahrens werden in der Regel von 1 bis 99 Mol-% S-Vinylthioalkanol, bevorzugt von 20 bis 80 Mol-%, besonders bevorzugt von 30 bis 70 Mol-%, bezogen auf die Gesamtmenge an Monomeren eingesetzt.The amount of S-vinylthioalkanol used in the process of the invention may vary over a wide range depending on the application of the polymer. In the context of the process according to the invention, as a rule from 1 to 99 mol% of S-vinylthioalkanol, preferably from 20 to 80 mol%, particularly preferably from 30 to 70 mol%, based on the total amount of monomers used.

Entsprechend werden im Rahmen des erfindungsgemäßen Verfahrens von 1 bis 99 Mol-% S-Vinyl-2-thioethan-1-ol, bevorzugt 20 bis 80 Mol%, besonders bevorzugt 30 bis 70 Mol% und von 99 bis 1 Mol-% bevorzugt 80 bis 20 Mol%, besonders bevorzugt 70 bis 30 Mol% weitere Monomeren bezogen auf die Gesamtmenge an Monomeren eigesetzt. Insbesondere werden von 1 bis 99 Mol-% S-Vinyl-2-thioethan-1-ol, bevorzugt von 20 bis 80 Mol-%, besonders bevorzugt von 30 bis 70 Mol-% und von 99 bis 1 Mol-% bevorzugt von 80 bis 20 Mol-%, besonders bevorzugt von 70 bis 30 Mol-% Acrylsäure bezogen auf die Gesamtmenge an Monomeren eingesetzt.Accordingly, from 1 to 99 mol% of S-vinyl-2-thioethane-1-ol, preferably from 20 to 80 mol%, particularly preferably from 30 to 70 mol%, and from 99 to 1 mol% is preferred in the process according to the invention to 20 mol%, particularly preferably 70 to 30 mol%, of further monomers based on the total amount of monomers. In particular, from 1 to 99 mol% of S-vinyl-2-thioethane-1-ol, preferably from 20 to 80 mol%, more preferably from 30 to 70 mol%, and from 99 to 1 mol%, preferably from 80 used to 20 mol%, particularly preferably from 70 to 30 mol% of acrylic acid based on the total amount of monomers.

Ein weiterer Gegenstand der Erfindung sind Polymere, hergestellt nach dem erfindungsgemäßen Verfahren, bevorzugt hydrolysestabile Polymere.
Ein weiterer Gegenstand der Erfindung sind Copolymere, bevorzugt hydrolysestabile Copolymere, bestehend aus S-Vinyl-2-thioethan-1-ol und einem oder mehreren ethylenisch ungesättigten Monomeren gewählt aus der Gruppe bestehend aus Acrylsäure, Itaconsäure, Maleinsäure, Maleinsäureanhydrid, Vinylphosphonäure. Bevorzugt sind Copolymere bestehend aus S-Vinyl-2-thioethan-1-ol und Acrylsäure.Another object of the invention are polymers prepared by the process according to the invention, preferably hydrolysis-stable polymers.
Another object of the invention are copolymers, preferably hydrolysis-stable copolymers consisting of S-vinyl-2-thioethan-1-ol and one or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid, itaconic acid, maleic acid, maleic anhydride, vinylphosphonic acid. Preference is given to copolymers consisting of S-vinyl-2-thioethane-1-ol and acrylic acid.

Ein weiterer Gegenstand der Erfindung sind Mischungen, bevorzugt wässrige Zusammensetzungen, enthaltend die oben genannten Polymere, die nach dem erfindungsgemäßen Verfahren hergestellt wurden. Bevorzugt sind wässrige Zusammensetzungen die mindestens 50 Gew.-% Wasser enthalten, besonders bevorzugt mindestens 80 Gew.-% Wasser, insbesondere 100 Gew.-% Wasser bezogen auf die Gesamtmenge an Lösemittel. Diese Mischungen bzw. wässrigen Zusammensetzungen weisen einen pH von 2 bis 10, besonders bevorzugt einen pH von 4 bis 8, insbesondere einen pH von 5 bis 7 auf.Another object of the invention are mixtures, preferably aqueous compositions containing the above-mentioned polymers, which were prepared by the process according to the invention. Preference is given to aqueous compositions which contain at least 50% by weight of water, particularly preferably at least 80% by weight of water, in particular 100% by weight of water, based on the total amount of solvent. These mixtures or aqueous compositions have a pH of from 2 to 10, particularly preferably a pH of from 4 to 8, in particular a pH of from 5 to 7.

Ein weiterer Gegenstand der Erfindung ist die Verwendung der oben genannten Polymere, die nach dem erfindungsgemäßen Verfahren hergestellt wurden, oder von Mischungen, bevorzugt wässrige Zusammensetzungen, enthaltend solche Polymere als Betonverflüssiger, Netzmittel, in der Kosmetik, als Klebstoffbestandteil, in der Emulsionspolymerisation, zur Metalloberflächenbehandlung, in Beschichtungsanwendungen, in Lacken, in Waschmitteln, in Spülmitteln, als Verkapselungsmaterial oder Umhüllungsmaterial.The invention further provides the use of the abovementioned polymers prepared by the process according to the invention or of mixtures, preferably aqueous compositions containing such polymers as concrete plasticizers, wetting agents, in cosmetics, as adhesive components, in emulsion polymerization, for metal surface treatment , in coating applications, in paints, in detergents, in dishwashing detergents, as encapsulating material or wrapping material.

Die vorliegende Erfindung stellt reaktive hydrolysestabile S-Vinylthioalkanole bereit, die sich effizient zu hydrolysestabilen Polymeren und Copolymeren umsetzen lassen. Die Polymere und Copolymere sind ebenfalls weitgehend stabil gegen Basen und Säuren bezüglich einer Hydrolyse an der Hydroxyalkylgruppe. Die S-Vinylthioalkanole eignen sich daher beispielsweise als hydrolysestabiler Ersatz von Hydroxyalkyl(meth)acrylaten.The present invention provides reactive hydrolysis-stable S-vinylthioalkanols which can be efficiently reacted to give hydrolysis-stable polymers and copolymers. The polymers and copolymers are also largely stable to bases and acids with respect to hydrolysis at the hydroxyalkyl group. The S-vinylthioalkanols are therefore suitable, for example, as hydrolysis-stable replacement of hydroxyalkyl (meth) acrylates.

Beispielsweise liegt Hydroxyethylacrylat bei pH 13 in Wasser nach 60 min zu ca. 70% hydrolysiert vor, S-Vinyl-2-thioethan-1-ol hydrolisiert unter diesen basischen Bedingungen kaum.For example, at pH 13 in water, hydroxyethyl acrylate is approximately 70% hydrolyzed after 60 minutes; S-vinyl-2-thioethane-1-ol barely hydrolyzes under these basic conditions.

Insbesondere sind diese Monomere bei der radikalischen Polymerisation in wässiger Lösung sowie die entstehenden Polymere bei der Lagerung in wässriger Lösung stabil. Analoge Vinyletheralkohole sind nämlich nicht hydrolysestabil beim radikalischen Polymerisieren in Wasser - in Gegenwart von Säuren entsteht Acetaldehyd und das entsprechende Diol, jedoch kein Polymer.In particular, these monomers are stable in the free-radical polymerization in aqueous solution and the resulting polymers when stored in aqueous solution. Namely, analogous vinyl ether alcohols are not stable to hydrolysis on radical polymerisation in water - acetaldehyde and the corresponding diol are formed in the presence of acids, but not a polymer.

Auch sind die S-Vinylthioalkanole sogar hydrolysestabil beim Copolymerisieren (sogar mit Säuren wie Acrylsäure oder Itaconsäure) und Lagern der Copolymere in wässriger Lösung.Also, the S-vinylthioalkanols are even stable to hydrolysis upon copolymerization (even with acids such as acrylic acid or itaconic acid) and storage of the copolymers in aqueous solution.

Die Erfindung wird durch die Beispiele näher erläutert ohne dass die Beispiele den Gegenstand der Erfindung einschränken.The invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.

Beispiele:Examples: Messmethoden:Measurement Methods: K-Werte:K values:

Die K-Werte wurden nach H. Fikentscher, Cellulose-Chemie, Bd. 13, Seiten 58 bis 64 und 71 bis 74 (1932 ) in 1 Gew.-%iger wässriger bzw. methanolischer Lösung bei 25°C gemessen.The K values were after H. Fikentscher, Cellulose Chemistry, Vol. 13, pages 58 to 64 and 71 to 74 (1932 ) in 1 wt .-% aqueous or methanolic solution at 25 ° C.

GPC-Messung:GPC measurement:

Die GPC Messungen wurden in N,N-Dimethylacetamid (DMAC) mit Polymethylmethacrylat (PMMA) (Molekulargewichtsverteilung von von M = 800 bis M = 1.820.000) als Standard durchgeführt. Verwendete Säulen: Säulen Trennmaterial Ausschlußgrenze Bezeichnung Durchmesser Länge mm cm g/mol 8 5 Polyester copolymer GRAM Vorsäule 8 30 Polyester copolymer 100-10.000 GRAM 30A 8 30 Polyester copolymer 1000 -1.000.000 GRAM 1000A 8 30 Polyester copolymer 1000 -1.000.000 GRAM 1000A The GPC measurements were carried out in N, N-dimethylacetamide (DMAC) with polymethyl methacrylate (PMMA) (molecular weight distribution of from M = 800 to M = 1,820,000) as standard. Used columns: columns separating material exclusion limit description diameter length mm cm g / mol 8th 5 Polyester copolymer GRAM guard column 8th 30 Polyester copolymer 100-10000 GRAM 30A 8th 30 Polyester copolymer 1000 -1.000.000 GRAM 1000A 8th 30 Polyester copolymer 1000 -1.000.000 GRAM 1000A

Beispiel 1: Herstellung S-Vinyl-2-thioethan-1-ol /Acrylsäure Copolymer (Verhältnis 50 mol/50 mol)Example 1: Preparation of S-vinyl-2-thioethane-1-ol / acrylic acid copolymer (ratio 50 mol / 50 mol)

In einem Reaktorgefäß, das mit Rührer, Temperaturkontrolle, Stickstoffeinleitung und mehreren Zulaufstellen versehen war, wurden 58,0g entionisiertes Wasser, 1,3 g von Zulauf 1, 1,2 g von Zulauf 2 und 1,1g von Zulauf 3 vorgelegt.

  • Zulauf 1: 26g S-Vinyl-2-thioethan-1-ol.
  • Zulauf 2: 18g Acrylsäure und 6g entionisiertes Wasser.
  • Zulauf 3: 1,32 g Azo-Initiator (2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochlorid, Wako VA-044) und 20g entionisiertes Wasser.
In a reactor vessel equipped with stirrer, temperature control, nitrogen inlet and several feed points, 58.7 g of deionized water, 1.3 g of feed 1, 1.2 g of feed 2 and 1.1 g of feed 3 were introduced.
  • Feed 1: 26 g of S-vinyl-2-thioethane-1-ol.
  • Feed 2: 18 g of acrylic acid and 6 g of deionized water.
  • Feed 3: 1.32 g of azo initiator (2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, Wako VA-044) and 20 g of deionized water.

Die Vorlage wurde 15 Minuten mit Stickstoff begast und unter Stickstoffatmosphäre auf 70 °C erhitzt. Anschließend wurde innerhalb von 3 Stunden der Rest von Zulauf 1 und von Zulauf 2 sowie innerhalb von 4 Stunden der Rest von Zulauf 3 zugetropft.The template was sparged with nitrogen for 15 minutes and heated to 70 ° C. under a nitrogen atmosphere. Subsequently, the remainder of feed 1 and of feed 2 and within 4 hours the remainder of feed 3 was added dropwise within 3 hours.

Danach wurde 2 Stunden bei 70°C gerührt. Man erhielt eine hellgelbe, klare Polymerlösung mit einem Feststoffgehalt von 29,8% und einem K-Wert von 23,2 (1 % in Methanol).Thereafter, the mixture was stirred at 70 ° C for 2 hours. This gave a light yellow, clear polymer solution having a solids content of 29.8% and a K value of 23.2 (1% in methanol).

Per GPC wurde Mn zu 3348 g/mol, Mw zu 6026 g/mol und PDI (Mw/Mn) zu 1,8 bestimmt (Eichkurve für PMMA).By GPC, Mn was determined to be 3348 g / mol, Mw to 6026 g / mol, and PDI (Mw / Mn) to 1.8 (calibration curve for PMMA).

Weder Restmonomer noch Hydrolyseprodukte von S-Vinyl-2-thioethan-1-ol konnten per 1H-NMR Spektroskopie detektiert werden. Zur Detektion potentieller Hydrolyseprodukte wurden zusätzlich 1H-NMR-Aufstockversuche mit 2-Thioethan-1-ol sowie Ethylenglycol durchgeführt.Neither residual monomer nor hydrolysis products of S-vinyl-2-thioethan-1-ol could be detected by 1 H NMR spectroscopy. For the detection of potential hydrolysis products 1 H-NMR Aufstockversuche with 2-thioethane-1-ol and ethylene glycol were performed.

Die obere kritische Lösungstemperatur (upper critical solution temperature, UCST) des Copolymers in Wasser betrug ca. 50°C.The upper critical solution temperature (UCST) of the copolymer in water was about 50 ° C.

Beispiel 2: Herstellung S-Vinyl-2-thioethan-1-ol /Acrylsäure Copolymer (Verhältnis 40 mol/60 mol)Example 2: Preparation of S-vinyl-2-thioethane-1-ol / acrylic acid copolymer (ratio 40 mol / 60 mol)

In einem Reaktorgefäß, das mit Rührer, Temperaturkontrolle, Stickstoffeinleitung und mehreren Zulaufstellen versehen war, wurden 63,8g entionisiertes Wasser, 1,5 g von Zulauf 1, 2,5 g von Zulauf 2 und 1,6g von Zulauf 3 vorgelegt.

  • Zulauf 1: 29,2g S-Vinyl-2-thioethan-1-ol.
  • Zulauf 2: 30,3g Acrylsäure und 20,0g entionisiertes Wasser.
  • Zulauf 3: 1,8 g Wako VA-044 und 30g entionisiertes Wasser.
In a reactor vessel equipped with stirrer, temperature control, nitrogen inlet and several feed points, 63.8 g of deionized water, 1.5 g of feed 1, 2.5 g of feed 2 and 1.6 g of feed 3 were introduced.
  • Feed 1: 29.2 g of S-vinyl-2-thioethane-1-ol.
  • Feed 2: 30.3 g of acrylic acid and 20.0 g of deionized water.
  • Feed 3: 1.8 g of Wako VA-044 and 30 g of deionized water.

Die Vorlage wurde 15 Minuten mit Stickstoff begast und unter Stickstoffatmosphäre auf 70 °C erhitzt. Anschließend wurde innerhalb von 3 Stunden der Rest von Zulauf 1 und von Zulauf 2 sowie innerhalb von 4 Stunden der Rest von Zulauf 3 zugetropft.The template was sparged with nitrogen for 15 minutes and heated to 70 ° C. under a nitrogen atmosphere. Subsequently, the remainder of feed 1 and of feed 2 and within 4 hours the remainder of feed 3 was added dropwise within 3 hours.

Danach wurde 2 Stunden bei 70°C gerührt. Man erhielt eine hellgelbe, klare Polymerlösung mit einem Feststoffgehalt von 27,6% und einem K-Wert von 24,7 (1 % in Methanol).Thereafter, the mixture was stirred at 70 ° C for 2 hours. A light yellow, clear polymer solution having a solids content of 27.6% and a K value of 24.7 (1% in methanol) was obtained.

Weder Restmonomer noch Hydrolyseprodukte von S-Vinyl-2-thioethan-1-ol konnten per 1H-NMR Spektroskopie detektiert werden. Zur Detektion potentieller Hydrolyseprodukte wurden zusätzlich 1H-NMR-Aufstockversuche mit 2-Thioethan-1-ol sowie Ethylenglycol durchgeführt.Neither residual monomer nor hydrolysis products of S-vinyl-2-thioethan-1-ol could be detected by 1 H NMR spectroscopy. For the detection of potential hydrolysis products 1 H-NMR Aufstockversuche with 2-thioethane-1-ol and ethylene glycol were performed.

Die obere kritische Lösungstemperatur (upper critical solution temperature, UCST) des Copolymers in Wasser betrug ca. 37°C.The upper critical solution temperature (UCST) of the copolymer in water was about 37 ° C.

Beispiel 3: Herstellung S-Vinyl-2-thioethan-1-ol HomopolymerExample 3: Preparation of S-vinyl-2-thioethan-1-ol homopolymer

In einem Reaktorgefäß, das mit Rührer, Temperaturkontrolle, Stickstoffeinleitung und mehreren Zulaufstellen versehen war, wurden 29,8g entionisiertes Wasser, 30,0g Ethanol, 2,0 g von Zulauf 1 und 1,1g von Zulauf 2 vorgelegt.

  • Zulauf 1: 41,7g S-Vinyl-2-thioethan-1-ol.
  • Zulauf 2: 1,25 g Wako VA-044 und 20g entionisiertes Wasser.
  • Zulauf 3: 0,83g Wako VA-044 und 13,33g Wasser.
In a reactor vessel equipped with stirrer, temperature control, nitrogen inlet and several feed points, 29.8 g of deionized water, 30.0 g of ethanol, 2.0 g of feed 1 and 1.1 g of feed 2 were introduced.
  • Feed 1: 41.7 g of S-vinyl-2-thioethane-1-ol.
  • Feed 2: 1.25 g Wako VA-044 and 20 g deionized water.
  • Feed 3: 0.83g Wako VA-044 and 13.33g water.

Die Vorlage wurde 15 Minuten mit Stickstoff begast und unter Stickstoffatmosphäre auf 70 °C erhitzt. Anschließend wurd innerhalb von 3 Stunden der Rest von Zulauf 1 sowie innerhalb von 4 Stunden der Rest von Zulauf 2 zugetropft. Danach wurd 2 Stunden bei 70°C gerührt. Anschließend wurd Zulauf 3 innerhalb von 45 min zugetropft und 2 Stunden bei 70°C gerührt.The template was sparged with nitrogen for 15 minutes and heated to 70 ° C. under a nitrogen atmosphere. Subsequently, the remainder of feed 1 and within 4 hours the remainder of feed 2 were added dropwise within 3 hours. Thereafter, the mixture was stirred at 70 ° C for 2 hours. Subsequently, feed 3 was added dropwise within 45 min and stirred at 70 ° C for 2 hours.

Man erhielt ein hellgelbe, klare Polymerlösung mit einem Feststoffgehalt von 28,3% und einem K-Wert von 23,3 (1 % in Methanol).A light yellow, clear polymer solution having a solids content of 28.3% and a K value of 23.3 (1% in methanol) was obtained.

Der Restmonomergehalt betrug ca. 2 mol% bezogen auf die eingesetzte Gesamtmonomermenge. Per GPC wurde Mn auf 6718 g/Mol, Mw auf 16680 g/mol und der PDI auf 2,5 bestimmt. (Eichkurve für PMMA).The residual monomer content was about 2 mol%, based on the total amount of monomers used. Mn was determined to be 6718 g / mol per GPC, Mw to 16680 g / mol and PDI to 2.5. (Calibration curve for PMMA).

Beispiel 4: Herstellung S-Vinyl-2-thioethan-1-ol /Acrylsäure Copolymer (Verhältnis 10 mol/90 mol)Example 4: Preparation of S-vinyl-2-thioethane-1-ol / acrylic acid copolymer (ratio 10 mol / 90 mol)

In einem Reaktorgefäß, das mit Rührer, Temperaturkontrolle, Stickstoffeinleitung und mehreren Zulaufstellen versehen war, wurden 73,6g entionisiertes Wasser, 6,0 g von Zulauf 1 und 2,25 g von Zulauf 2 vorgelegt.

  • Zulauf 1: 77,82g Acrylsäure, 12,50g S-Vinyl-2-thioethan-1-ol, 30,0g entionisiertes Wasser.
  • Zulauf 2: 5,42 g Azoinitiator (2,2'-Azobis(2-methylpropionamidine)dihydrochloride, Wako V-50) und 40,0g entionisiertes Wasser.
73.6 g of deionized water, 6.0 g of feed 1 and 2.25 g of feed 2 were placed in a reactor vessel equipped with stirrer, temperature control, nitrogen inlet and several feed points.
  • Feed 1: 77.82 g of acrylic acid, 12.50 g of S-vinyl-2-thioethane-1-ol, 30.0 g of deionized water.
  • Feed 2: 5.42 g of azo initiator (2,2'-azobis (2-methylpropionamidine) dihydrochloride, Wako V-50) and 40.0 g of deionized water.

Die Vorlage wurde 15 Minuten mit Stickstoff begast und unter Stickstoffatmosphäre auf 88 °C erhitzt. Anschließend wurde innerhalb von 3 Stunden der Rest von Zulauf 1 sowie innerhalb von 4 Stunden der Rest von Zulauf 2 zugetropft. Danach wurde 2 Stunden bei 88°C gerührt.The template was sparged with nitrogen for 15 minutes and heated to 88 ° C under a nitrogen atmosphere. Subsequently, the remainder of feed 1 was added dropwise within 3 hours, and the remainder of feed 2 was added dropwise within 4 hours. Thereafter, the mixture was stirred at 88 ° C for 2 hours.

Man erhielt eine hellgelbe, klare Polymerlösung mit einem Feststoffgehalt von 40,6% und einem K-Wert von 12,7 (1% in Wasser).A light yellow, clear polymer solution having a solids content of 40.6% and a K value of 12.7 (1% in water) was obtained.

Weder Restmonomer noch Hydrolyseprodukte von S-Vinyl-2-thioethan-1-ol konnten per 1H-NMR Spektroskopie detektiert werden. Zur Detektion potentieller Hydrolyseprodukte wurden zusätzlich 1H-NMR-Aufstockversuche mit 2-Thioethan-1-ol sowie Ethylenglycol durchgeführt.Neither residual monomer nor hydrolysis products of S-vinyl-2-thioethan-1-ol could be detected by 1 H NMR spectroscopy. For the detection of potential hydrolysis products 1 H-NMR Aufstockversuche with 2-thioethane-1-ol and ethylene glycol were performed.

Beispiel 5: Herstellung S-Vinyl-2-thioethan-1-ol /Acrylsäure Copolymer (Verhältnis 20 mol/80 mol)Example 5: Preparation of S-vinyl-2-thioethane-1-ol / acrylic acid copolymer (ratio 20 mol / 80 mol)

In einem Reaktorgefäß, das mit Rührer, Temperaturkontrolle, Stickstoffeinleitung und mehreren Zulaufstellen versehen war, wurden 79,75g entionisiertes Wasser, 6,2 g von Zulauf 1 und 2,3 g von Zulauf 2 vorgelegt.

  • Zulauf 1: 69,18g Acrylsäure, 25,0g S-Vinyl-2-thioethan-1-ol, 30,0g entionisiertes Wasser.
  • Zulauf 2: 5,65 g Wako V-50 und 40,0g entionisiertes Wasser.
In a reactor vessel equipped with stirrer, temperature control, nitrogen inlet and several feed points, 79.75 g of deionized water, 6.2 g of feed 1 and 2.3 g of feed 2 were introduced.
  • Feed 1: 69.18 g of acrylic acid, 25.0 g of S-vinyl-2-thioethane-1-ol, 30.0 g of deionized water.
  • Feed 2: 5.65 g Wako V-50 and 40.0 g deionized water.

Die Vorlage wurde 15 Minuten mit Stickstoff begast und unter Stickstoffatmosphäre auf 88 °C erhitzt. Anschließend wurde innerhalb von 3 Stunden der Rest von Zulauf 1 sowie innerhalb von 4 Stunden der Rest von Zulauf 2 zugetropft. Danach wurd 2 Stunden bei 88°C gerührt.The template was sparged with nitrogen for 15 minutes and heated to 88 ° C under a nitrogen atmosphere. Subsequently, the remainder of feed 1 was added dropwise within 3 hours, and the remainder of feed 2 was added dropwise within 4 hours. Thereafter, the mixture was stirred at 88 ° C for 2 hours.

Man erhielt eine hellgelbe, klare Polymerlösung mit einem Feststoffgehalt von 39,2% und einem K-Wert von 10,5 (1 % in Wasser).A light yellow, clear polymer solution having a solids content of 39.2% and a K value of 10.5 (1% in water) was obtained.

Weder Restmonomer noch Hydrolyseprodukte von S-Vinyl-2-thioethan-1-ol konnten per 1H-NMR Spektroskopie detektiert werden. Zur Detektion potentieller Hydrolyseprodukte wurden zusätzlich 1H-NMR-Aufstockversuche mit 2-Thioethan-1-ol sowie Ethylenglycol durchgeführt.Neither residual monomer nor hydrolysis products of S-vinyl-2-thioethan-1-ol could be detected by 1 H NMR spectroscopy. For the detection of potential hydrolysis products 1 H-NMR Aufstockversuche with 2-thioethane-1-ol and ethylene glycol were performed.

Beispiel 6: Herstellung S-Vinyl-2-thioethan-1-ol /Acrylsäure / Itaconsäure / Vinylphosphonsäure Copolymer (Verhältnis 5 mol / 55 mol / 30 mol / 10 mol)Example 6 Preparation of S-vinyl-2-thioethane-1-ol / acrylic acid / itaconic acid / vinylphosphonic acid copolymer (ratio 5 mol / 55 mol / 30 mol / 10 mol)

In einem Reaktorgefäß, das mit Rührer, Temperaturkontrolle, Stickstoffeinleitung und mehreren Zulaufstellen versehen war, wurden 42,67g entionisiertes Wasser, 9,32 g Vinylphosphonsäure (95%ig) und 32,0 g Itaconsäure vorgelegt. Die Vorlage wurd 15 Minuten mit Stickstoff begast und unter Stickstoffatmosphäre auf 98 °C erhitzt. Anschließend wurd innerhalb von 5 Stunden 32,5g Acrylsäure, 4,3g S-Vinyl-2-thioethan-1-ol und 30,0g entionisiertes Wasser sowie innerhalb von 6 Stunden 3,1g Wako V-50 und 48,0 g entionisiertes Wasser zugetropft. Danach wurde 2 Stunden bei 98°C gerührt.In a reactor vessel equipped with stirrer, temperature control, nitrogen inlet and several feed points, 42.67 g of deionized water, 9.32 g of vinylphosphonic acid (95%) and 32.0 g of itaconic acid were introduced. The template was gassed with nitrogen for 15 minutes and heated to 98 ° C. under a nitrogen atmosphere. Subsequently, within 5 hours 32.5 g of acrylic acid, 4.3 g of S-vinyl-2-thioethan-1-ol and 30.0 g of deionized water and within 6 hours 3.1 g Wako V-50 and 48.0 g of deionized water dropwise. Thereafter, the mixture was stirred at 98 ° C for 2 hours.

Man erhielt eine gelbe, klare Polymerlösung mit einem Feststoffgehalt von 39,9% und einem K-Wert von 13,0 (1 % in Wasser). 2,9 mol% Vinylphosphonsäure bezogen auf die Gesamtmenge an eingesetzter Vinylphosphonsäure konnten im 1H- und 31P-NMR Spektrum detektiert werden.A yellow, clear polymer solution having a solids content of 39.9% and a K value of 13.0 (1% in water) was obtained. 2.9 mol% of vinylphosphonic acid, based on the total amount of vinylphosphonic acid used, could be detected in the 1 H and 31 P NMR spectrum.

Beispiel 7: AnwendungsbeispieleExample 7: Application Examples

Die Copolymere aus Beispiel 4 und 5 wurden zur Beschichtung von Prüfblechen aus heiß verzinktem Stahl (Gardobond OE HDG 3; 105 x 190 m) eingesetzt.The copolymers of Examples 4 and 5 were used to coat hot galvanized steel test panels (Gardobond OE HDG 3, 105 x 190 m).

Als Vorbehandlung wurden die Prüfbleche in einer mild alkalischen Reinigerlösung (Surtech 133, Fa. Surtech) für 30 Sekunden getaucht, sofort mit voll entsalztem Wasser abgespült und anschließend mit Stickstoff getrocknet. Die gereinigten Bleche wurden für 1 Sekunde in eine 25 Gew.-%ige wässrige Lösung des Copolymeren getaucht, mit einem Walzensystem abgequetscht und für 12 Sekunden bei 160°C im Umluft-Trockenschrank getrocknet. Die Peak-Metal-Temperature (PMT) überstieg hierbei nicht 50°C.As a pretreatment, the test panels were immersed in a mildly alkaline cleaner solution (Surtech 133, Surtech) for 30 seconds, rinsed immediately with demineralized water and then dried with nitrogen. The cleaned sheets were immersed for 1 second in a 25 wt .-% aqueous solution of the copolymer, squeezed off with a roller system and dried for 12 seconds at 160 ° C in a convection oven. The peak metal temperature (PMT) did not exceed 50 ° C.

Die so erhaltenen Prüfbleche wurden hinsichtlich ihrer Korrosionsbeständigkeit in einem Salzsprühtest nach DIN EN ISO 9227 untersucht. Polymer korrodierte Fläche nach Salzsprühtest keine Beschichtung 100 % (vollständig korrodiert) AS/ S-Vinyl-2-thioethan-1-ol 90/10 ca. 30 % AS/ S-Vinyl-2-thioethan-1-ol 80/20 ca. 10 % The test panels thus obtained were examined for their corrosion resistance in a salt spray test according to DIN EN ISO 9227. polymer Corroded area after salt spray test no coating 100% (completely corroded) AS / S-vinyl-2-thioethane-1-ol 90/10 about 30% AS / S-vinyl-2-thioethane-1-ol 80/20 about 10%

Die Daten belegen die passivierende Wirkung durch die erfindungsgemäßen Copolymere.The data substantiate the passivating effect by the copolymers according to the invention.

Claims (14)

  1. A process for preparing a polymer comprising S-vinylthioalkanol as monomer by radical polymerization, which comprises carrying out the polymerization in aqueous solution, with the proviso that no N-vinylpyrrolidone is used as monomer for preparing the polymer, and wherein at least one further monomer, different from an S-vinylthioalkanol, is used, the further monomer being a monoethylenically unsaturated water-soluble monomer, with the exception of vinylpyrrolidone.
  2. The process according to claim 1, wherein as S-vinylthioalkanol unsaturated compounds of the general formula (I) are used
    Figure imgb0003
     where
    R1, R2, and R3 independently of one another, identically or differently, are H or CH3 and
    R4 is linear or branched C1-C30 alkylene.
  3. The process according to claim 1 or 2, wherein the S-vinylthioalkanol is selected from the group consisting of S-vinyl-2-thioethan-1-ol, S-vinyl-2-thiopropan-1-ol, S-vinyl-1-thiopropan-2-ol, S-vinyl-2-thiobutan-1-ol, S-vinyl-1-thiobutan-2-ol, S-vinyl-2-thiopentan-1-ol, S-vinyl-1-thiopentan-2-ol, S-vinyl-2-thiocyclohexan-1-ol, S-vinyl-2-thio-(C12-C22)-1-ol, S-vinyl-1-thio-(C12-C22)-2-ol, S-vinyl-1-thiopropane-2,3-diol, S-vinyl-2-thiopropane-1,3-diol, 1-phenyl-S-vinyl-1-thioethan-2-ol, and 1-phenyl-S-vinyl-2-thioethan-1-ol.
  4. The process according to claim 3, wherein at least one monomer is selected from the group consisting of monoethylenically unsaturated water-soluble monomer having one or more acid groups, monoethylenically unsaturated water-soluble monomer having one or more ester groups, monoethylenically unsaturated water-soluble monomer having one or more amide groups, monoethylenically unsaturated water-soluble monomer having one or more anhydride groups, monoethylenically unsaturated water-soluble monomer having one or more quaternized nitrogen groups, and monoethylenically unsaturated water-soluble monomer having one or more heteroaromatic groups.
  5. The process according to claim 4, wherein as at least one monoethylenically unsaturated monomer acrylic acid is used.
  6. The process according to claim 5, wherein besides S-vinyl-2-thioethan-1-ol and acrylic acid no further monomers are used.
  7. The process according to claims 1 to 6, wherein the resultant polymer has an upper critical solution temperature in water of 0 to 99°C.
  8. The process according to claims 1 to 7, wherein from 1 to 99 mol% of S-vinylthioalkanol is used, based on the total amount of monomers.
  9. The process according to claims 3 to 7, wherein from 1 to 99 mol% of S-vinyl-2-thioethan-1-ol and from 99 to 1 mol% of further monomers are used, based on the total amount of monomers.
  10. The process according to claim 6, wherein from 1 to 99 mol% of S-vinyl-2-thioethan-1-ol and from 99 to 1 mol% of acrylic acid is used, based on the total amount of monomers.
  11. A polymer comprising S-vinylthioalkanol as monomer and at least one further monomer, different from an S-vinylthioalkanol, the further monomer being a monoethylenically unsaturated water-soluble monomer, with the exception of vinylpyrrolidone, prepared by a process according to claims 1 to 10.
  12. A copolymer consisting of S-vinyl-2-thioethan-1-ol and one or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid, itaconic acid, maleic acid, maleic anhydride, and vinylphosphonic acid.
  13. A mixture, preferably aqueous composition, comprising polymer according to claim 11 or 12.
  14. The use of polymer according to claim 11 or 12 or of aqueous composition according to claim 13 as concrete plasticizer, wetting agent, in cosmetics, as adhesive constituent, in emulsion polymerization, for metal surface treatment, in coating applications, in paints, in laundry detergents, in washing detergents, as encapsulating material or as enveloping material.
EP14780872.9A 2013-10-30 2014-10-06 Polymers containing s-vinylthioalkanoles Not-in-force EP3063191B1 (en)

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DE2048664C3 (en) * 1970-10-03 1980-08-14 Basf Ag, 6700 Ludwigshafen Water-soluble, high molecular weight copolymers and their use as paper auxiliaries
DE2055893A1 (en) 1970-11-13 1972-05-18 Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen Process for the production of coatings by curing by means of ionizing radiation
DE2058120A1 (en) 1970-11-26 1972-05-31 Basf Ag Cationic copolymers of ethylenically unsaturated cpds - used as paper sizings and textile dressings
DE2128681A1 (en) 1971-06-09 1972-12-21 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Stoving lacquer - based on aminoplast and a copolymer contg a sulphonium-salt
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